Compound with branching alkyl chains, method for preparing the same, and use thereof in photoelectric device

ABSTRACT

The invention discloses a compound having branching alkyl chains, the method for preparing the same and use thereof in photoelectric devices. By applying the branching alkyl chains as the solubilizing group to the preparation of organic conjugated molecules (for example, organic conjugated polymers), the number of methylenes between the resultant alkyl side chains and the backbone, i.e., m&gt;1, which can effectively reduce the effect of the alkyl chains on the backbone π-π stacking, thereby ensuring the solubility of the organic conjugated molecule while greatly increasing the mobility of their carriers. It is suitable for an organic semiconductor material in photoelectric devices such as organic solar cells, organic light emitting diodes and organic field effect transistors, etc.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 14/808,387. U.S. application Ser. No. 14/808,387 is a divisionalapplication of U.S. application Ser. No. 13/935,779, which claimspriority to Chinese National Application No. 201210232860.9 filed onJul. 5, 2012, the contents of which are incorporated herein byreference.

TECHNICAL FIELD

The invention relates to a compound with novel branching alkyl chainsand a method for preparing the same, in particularly, relates to a classof organic electronic material with branching alkyl chains and a methodfor preparing the same. The invention belongs to the field of organicfunctional material and the field of organic electronics.

BACKGROUND

The structure of an organic conjugated molecule comprises a conjucatedsystem consisting of delocalized π electrons, thereby presenting specialoptical, electric and magnetic properties, etc. which catches a wideattention of scientists and has become the focus of studies of the last20 years. Synthesis based on organic conjugated molecules andfunctionalization and instrumentalization studies involve many kinds ofdisciplines such as chemistry, physics, electronics, material sciences,etc. They are multidisciplinary frontiers, filled with vigor andopportunities, and are among one of the important directions of futuredevelopment of chemistry.

Due to their characteristics of lightness, thinness and flexibility,readiness for modification, etc., organic conjugated molecules havebroad prospects of application in the field of photoelectric material. Aseries of remarkable results have already been obtained, especially inthe fields of organic solar cell (OPV), organic light emitting diode(OLED) and organic field effect transistor (OFET), etc. Furthermore,since the organic field effect transistors have the characteristics ofreadiness for processing, low cost, capacity of large scale flexiblepreparation, readiness for integration, etc., present obvious advantagesin studies in the fields of electronic paper, electronic label, activematrix addressing, sensor and storage, etc., and are considered ashaving great market potentials.

The organic field effect transistor is an active device regulating theelectric circuit in an organic semiconductor by electric field. Itsmajor device structure comprises the 4 following classes: (1) bottomgate bottom contact (BG/BC); (2) top gate bottom contact (TG/BC); (3)bottom gate top contact (BG/TC); and (4) top gate top contact (TG/TC)(Di, C. A.; Liu, Y. Q.; Yu, G.; Zhu, D. B. Ace. Chem. Res., 2009, 42,1573). The organic field effect transistor consists essentially ofelectrodes, a dielectric layer, and an organic semiconductor layer, etc.It is essentially a capacitor carrying mobile charges. By applying avoltage between the gate electrode and the source electrode/drainelectrode, charges will be induced at the interface between thesemiconductor layer and the dielectric layer. When a small voltage isapplied between the two electrodes, i.e., the source electrode and thedrain electrode, an electric current is formed in the channel.Therefore, the magnitude of the induced charge at the interface can becontrolled by adjusting the magnitude of the gate electrode voltage toachieve the on/off of the device, and the amplification of the signal isachieved by controlling the magnitude of the electric current by thevoltage between the source electrode and the drain electrode.

The core of the organic field effect transistor is the organicsemiconductor layer. The organic semiconductor layer can be classifiedinto p type materials (transporting holes) and n type materials(transporting electrons) based on the difference of the carriertransported in the material; and it can also be classified into organicsmall molecular materials and organic conjugated polymer materials basedon the difference of the type of the organic conjugated molecules. Theorganic conjugated polymer has been highly regarded because it enablesthe preparation of the device at a large scale with low cost by solutionprocessing.

The studies on the p type polymer semiconductor materials were initiallyconcentrated on polythiophene systems. The mobility of a stericallyregular poly(3-hexylthiophene) (P3HT) can reach 0.05-0.2 ²V⁻¹s⁻¹(Sirringhaus, H.; Brown, P. J.; Friend, R. H.; Nielsen, M. M.;Bechgaard, K.; Langeveld-Voss, B. M. W.; Spiering, A. J. H.; Janssen, R.A. J.; Meijer, E. W.; Herwig, P.; de Leeuw, D. M. Nature, 1999, 401,685). Thereafter, more molecular construction units entered the radarscreen of the researchers. These new structures conferred new vigor intothis research area. For example, a mobility of 0.94 cm²V⁻¹s⁻¹ wasobtained for an organic conjugated polymer based ondiketo-pyrrolo-pyrrole (DPP) in 2010 (Li, Y.; Singh, S. P.; Sonar, P.Adv. Mater., 2010, 22, 4862). In 2011, Bronstein reported that amobility up to 1.94 cm²V⁻¹s⁻¹ was obtained for a DPP-based polymer bydifferent way of connection of the same construction blocks (Bronstein,H.; Chen, Z.; Ashraf, R. S.; Zhang, W.; Du, J.; Durrant, J. R.;Tuladhar, P. S.; Song, K.; Watkins, S. E.; Geerts, Y.; Wienk, M. M.;Janssen, R. A. J.; Anthopoulos, T.; Sirringhaus, H.; Heeney, M.;McCulloch, I. J. Am. Chem. Soc. 2011, 133, 3272). A compound obtained bythe copolymerization of DPP and thiophene presented a mobility of 0.97cm2V⁻¹s⁻¹. By a structural modification that used biselenophene toreplace bithiophene, a mobility of up to 1.5 cm²V⁻¹s⁻¹ was obtained (Ha,J. S., Kim, K. H., Choi, D. H. J. Am. Chem. Soc. 2011, 133, 10364).Isoindigo type molecules are a family of molecules of significance inaddition to DPP. In 2011, we reported that a mobility of 0.79 cm²V⁻¹s⁻¹and a device stability under high humidity up to 3 months were obtainedfor a polymer based on isoindigo structures (Lei, T.; Cao, Y.; Fan, Y.;Liu, C. J.; Yuan, S. C.; Pei, J. J. Am. Chem. Soc. 2011, 133, 6099).

In contrast, the development of n type polymer semiconductors isrelatively slow. Among them, Facchetti and Marks reported that anelectron mobility of 0.01 cm²V⁻¹s⁻¹ was obtained for a polymer based onthiophene and fluorobenzene (Letizia, J. A.; Facchetti, A.; Stern, C.L.; Ratner, M. A.; Marks, T. J. J. Am. Chem. Soc. 2005, 127, 13476).Zhan et al. reported that a copolymer based on perylene diimide anddithienothiophene exhibited a good field effect performance and itselectron mobility can reach 0.013 cm²V⁻¹s⁻¹ (Zhan, X.; Tan, Z.; Domereq,B.; An, Z.; Zhang, X.; Barlow, S.; Li, Y.; Zhu, D.; Kippelen, B.;Marder, S. R. J. Am. Chem. Soc. 2007, 129, 7246). Moreover, anaphthlenedicarboximide based polymer reported by Facchetti in 2009exhibited an electron mobility up to 0.85 cm²V⁻¹s⁻¹ (Chen, Z.; Zheng,Y.; Yan, H.; Facchetti, A. J. Am. Chem. Soc. 2009, 131, 8).

Compared to the traditional silicon solar cells, the organic solar cellshave the advantages of low cost, light weight, simple processing,readiness for large scale preparation and readiness for preparingflexible devices, etc. The structure of a device of an organicheterojunction solar cell is primarily classified into two types: one isthe forward cell and the other is the reverse cell. The forward cellconsists of an anode (generally ITO glass), a hole transport layer(generally PEDOT: PSS), active layer (composed of organic molecular suchas organic conjugated polymers and fullerene derivatives, etc.), anelectron transport layer, and a cathode (such as aluminum electrode).The reverse cell consists of a cathode (generally ITO glass), anelectron transport layer (generally oxide semiconductors such as zincoxide, etc.), an active layer (composed of organic molecular such asorganic conjugated polymers and fullerene derivatives, etc.), anelectron transport layer (generally semiconductors such as molybdenumtrioxide, etc.), and an anode (such as silver electrode). The activelayer is obtained by blending the two materials, i.e., the donor and theacceptor, and solution processing or evaporation them, in which theorganic conjugated polymer can serve as both the donor and the acceptor.In an ideal bulk heterojunction structure, the donor and the acceptorform an alternating co-continuous phase, which results in a microphaseseparation at a scale of tens of nanometers which not only can separatethe excitons generated by optical excitation with high efficiency, butalso can effectively transport the carriers after the exciton separationto the electrodes to generate the electric current (J. Peet, A. J.Heeger, G. C. Bazan, Ace. Chem. Res. 2009, 42, 1700).

In recent years, studies on the organic bulk heterojunction solar cellsbased on the solution processing of polymers have achieved remarkableresults. In 2007, Prof. Heeger et al. increased the power conversionefficiency of PCDTBT from 2.8% to 5.5% by controlling the morphology ofthe active layer with additives (J. Peet, J. Y. Kim, N. E. Coates, W. L.Ma, D. Moses, A. J. Heeger, G. C. Bazan, Nat. Mater. 2007, 6, 497), andin the same year, a laminated device was prepared which obtained anpower conversion efficiency of 6.5% (J. Y. Kim, K. Lee, N. E. Coates, D.Moses, T-Q Nguyen, M. Dante, A. L. Heeger, Science 2007, 317, 222). Yugroup of University of Chicago and Yang group of University ofCalifornia at Los Angeles reported a series of polymers based onthienothiophene and benzodithiophene structures and results of more than5% power conversion efficiency were obtained (Y. Liang, L. Yu, Acc.Chem. Res. 2010, 43, 1227). Moreover, for the first time a polymer bulkheterojuction solar cell with a power conversion efficiency of more than7% was reported, in which PTB7 achieved a power conversion efficiency upto 7.4% (Y. Liang, Z. Xu, J. Xia, S-T. Tsai, Y. Wu, G. Li, C. Ray, L,Yu, Adv. Mater. 2010, 22, E135). Cao group increased the powerconversion efficiency of PECz-DTQx from 4% to 6.07% using ITN modifiedelectrodes, and recently increased the efficiency of a bulkheterojunction solar cell with an inverted structure to 8.37% whichpassed the certification by National Center of Supervision andInspection on Solar Photovoltatic Products Quality (Z. He, C. Zhang, X.Huang, W-Y. Wong, H. Wu, L. Chen, S. Su, Y. Cao, Adv. Mater. 2011, 23,4636), and achieved the best results reported by current publications.Studies show that the efficiency of solar cells has close correlation tothe mobility rate of polymers. Generally, the higher the mobility of thepolymer, the higher of the efficiency of the solar cell (Chen, J.; Cao,Y. Acc. Chem. Res., 2009, 42, 1709). Therefore, increasing the mobilityof the polymer has great significance on the studies on solar cells.

Organic conjugated polymers are a class of polymers obtained bypolymerization of covalent bonds through conjugation from aromaticcompounds. In order to ensure their good solubility and solutionmanufacturability, at least one solubilizing group needs to beintroduced into at least one aromatic structure to increase theirsolubility. For example, the organic conjugated polymer as shown in thefollowing formula:

wherein Ar¹ and Ar² are fragments of aromatic compounds, respectively;R¹ and R² are solubilizing groups introduced into the aromatic core Ar¹,generally a group such as alkyl, halogen substituted alkyl, alkoxy,halogen substituted alkoxy, alkenyl, alkynyl, etc.; and n is the numberof the repeating unit of the polymer, i.e., polymerization degree.

In primary studies (Lei, T.; Cao, Y.; Zhou, X.; Peng, Y.; Bian, J.; Pei,J. Chem. Mater 2012, 24, 1762.), we found that if a solubilizing group(such as an alkyl chain) is distributed in every one of the polymerunits (as shown in FIG. 1(a)), it will affect the π-π stacking of thepolymerization, thereby greatly affecting the mobility of the carriersin the polymer. This is because the van der Waals' radius between alkylchains is 3.6-3.8 Å, while the distance of the π-π interaction is 3.4 Å(see the circle in FIG. 1(a) which indicates the repulsive effect of thealkyl chain against the aromatic group). As to this, we moved this alkylchain from the smaller aromatic core Ar² to the larger aromatic coreAr¹, thereby increasing the mobility. On the other hand, traditionally a2-branching alkyl chain (obtainable from Guerbet alcohol) is used as thesolubilizing group (such as FIG. 1(b)) to avoid affecting the π-πstacking so as to achieve high mobility (Li, Y. Acc. Chem. Res., 2012,45, 723; Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Chem. Rev, 2012,112, 2208; Beaujuge, P. M.; Fréchet J. M. J. J. Am. Chem. Soc. 2011,133, 20009; Wen, Y. Liu, Y. Adv. Mater. 2010, 22, 1331; Chen, J.; Cao,Y. Acc. Chem. Res., 2009, 42, 1709). The purpose of the design is toensure the π-π stacking while ensuring the solubility of the polymer.

SUMMARY

In view of the research efforts of the current polymer field effecttransistor material and the low mobility of the polymers in the solarcell material researches, the object of the application is to providecompounds containing a type of novel branching alkyl chains, and applythem to the preparation of organic conjugated molecules, especiallyorganic conjugated polymers. This novel branching alkyl chain ensuresthe solubility of the polymer while greatly increasing the mobility ofthe polymer material. This result has great significance on the polymerfield effect transistor. Meanwhile, this result can also be used forsmall molecular field effect transistor materials and not limited topolymer field effect transistors. Because of the important status of themobility of carriers in organic electronics, compounds and polymerscontaining these novel branching alkyl chains can also be applied toorganic solar cell materials, organic light emitting diode materials,and organic field effect transistor materials, etc.

In the first aspect of the invention, a compound containing a branchingalkyl chain having the general formula as shown in the following Formula(I) is provided:

The aforementioned structure is different from a Guerbet alcohol (m=1).In the structure of Formula (I), m is an integer more than 1; R can bevarious substituents, such as halogen atoms (F, Cl, Br, I), hydroxyl,amino, trifluoromethanesulfonate group (MsO), p-toluenesulfonate group(TsO), azide group (N₃), cyano, alkenyl, alkynyl, alkoxy, etc.; R³ andR⁴ are the same or different, independently selected from alkyl, halogensubstituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl andalkynyl; R⁵ is hydrogen, hydroxyl, alkyl, halogen substituted alkyl,alkoxy, halogen substituted alkoxy, alkenyl or alkynyl.

In Formula (I), m can, for example, be an integer of 2˜18, an integer of2˜10, an integer of 3˜18, an integer of 3˜10, an integer of 3˜5, or aninteger of 3˜4.

As a substituent of R, the alkenyl can, for example, be C2-C6 alkenyl,C2-C4 alkenyl, or ethenyl.

As a substituent of R, the alkynyl can, for example, be C2-C6 alkynyl,C2-C4 alkynyl, or ethynyl.

As a substituent of R, the alkoxy can, for example, be C1-C36 linear orbranching alkoxy, or C1-C18 linear or branching alkoxy.

As a substituent of R³, R⁴ and R⁵, the alkyl can, for example, be C1-C36linear or branching alkyl, or C1-C18 linear or branching alkyl.

As a substituent of R³, R⁴ and R⁵, the halogen substituted alkyl can,for example, be C1-C36 linear or branching halogen substituted alkyl, orC1-C18 linear or branching halogen substituted alkyl.

As a substituent of R³, R⁴ and R⁵, the alkoxy can for example, be C1-C36linear or branching alkoxy, or C1-C18 linear or branching alkoxy

As a substituent of R³, R⁴ and R⁵, the halogen substituted alkoxy can,for example, be C1-C36 linear or branching halogen substituted alkoxy,or C1-C18 linear or branching halogen substituted alkoxy.

As a substituent of R³, R⁴ and R⁵, the alkenyl can, for example, beC2-C18 alkenyl, C2-C10 alkenyl, or C2-C6 alkenyl.

As a substituent of R³, R⁴ and R⁵, the alkynyl can, for example, beC2-C18 alkynyl, C2-C10 alkynyl, or C2-C6 alkynyl.

Several specific examples of the aforementioned branching alkyl chainsare given below.

When R is hydroxyl, m=2, R³ and R⁴ are 10 carbon-atom alkyls, R⁵ is ahydrogen atom, the specific structure is as follows:

When R is halogen atom (such as 1), m=2, R³ and R⁴ are 10 carbon-atomalkyls, R⁵ is a hydrogen atom, the specific structure is as follows:

When R is hydroxyl, m=3, R³ and R⁴ are 14 carbon-atom alkyls, R⁵ is ahydrogen atom, the specific structure is as follows:

When R is hydroxyl, m=3, R³ and R⁴ are 18 carbon-atom alkyls, R⁵ is ahydrogen atom, the specific structure is as follows:

When R is amino, m=2, R³ and R⁴ are 10 carbon-atom alkyls, R⁵ is ahydrogen atom, the specific structure is as follows:

The procedure for preparing the compounds containing branching alkylchains as shown in Formula (1) is as follows:

(1) Starting from the diol as shown in Formula (a), protection by aprotecting group (sometimes is abbreviated as PG) is conducted:

In this step, the protecting group can be selected from benzyl (Bn),various silicon protecting groups (such as trimethylsilyl (TMS),triethylsilyl (TES), triisopropylsilyl (TIPS), t-butyldimethylsilyl(TBDMS), t-butyldiphenylsilyl (TBDPS), etc.), methoxymethyl protectinggroup (MOM), tetrahydropyran protecting group (THP), p-methoxyphenylprotecting group (PMB), etc., and the reaction is as follows:

(2) The diol with one terminus protected (Formula (b) compound) isoxidized to obtain the carboxylic acid as shown in Formula (c). Thisoxidation can be selected from various reactions that oxidize alcoholsto carboxylic acids, such as Jones oxidation (CrO₃—H₂SO₄) reaction, orperforming oxidation step by step (first oxidized into an aldehyde andthen oxidized into a carboxylic acid), etc.

(3) The carboxylic acid as shown in Formula (c) is subject to functionalgroup transformation and nucleophilic substitution to introduce the R³and R⁴ groups. Either of the following two methods can be selected:

(3a) The carboxylic acid is reacted with an alcohol (R′OH) and convertedinto an ester. This esterification can use various conditions, includingesterification under various acidic or alkaline conditions.Subsequently, a nucleophilic substitution is conducted to introduce theR³ and R⁴ groups.

The R′ is alkyl, for example, C1-C36 linear or branching alkyl, forexample, C1-C18 linear or branching alkyl, for example, C1-C8 linear orbranching alkyl.

The most commonly used nucleophilic substituting reagent is the Grignardreagent. The Formula (d) compound can be subject to one-stepnucleophilic substitution with the participation of correspondingGrignard reagents, and in the resulting Formula (e) compound, R³═R⁴.Also, by way of stepwise addition of different Grignard reagents,different R³ and R⁴ groups can be introduced.

(3b) The carboxylic acid is converted to an acyl halide including groupssuch as acyl chloride, acyl bromide etc., then the nucleophilicsubstitution can be conducted to introduce the R³ and R⁴ groups.

The X is halogen, for example, Cl and Br.

In Schemes (3a) and (3b), the nucleophilic substituting reagent, inaddition to the Grignard reagent, can be selected from othernucleophilic substituting reagents, such as alkyl lithium reagent(R³Li), alkyl copper lithium reagent (R³CuLi), etc.

(4) R⁵ is introduced using different methods according to differenttypes of the R⁵ group:

(4a) When R⁵ is alkoxy, a strong alkaline can react with an alcoholhydroxyl to generate an oxygen anion, which is subsequently subject to anucleophilic substutition by R⁵′X.

The X is a halogen atom (F, Cl, Br, I), trifluoromethanesulfonate groupor p-toluenesulfonate group.

The R⁵′ is selected from alkyl.

(4b)When R⁵ is alkyl, halogen substituted alkoxy, alkenyl or alkynyl,the Formula (e) compound can be first reacted withtrifluoromethanesulfonyl chloride to generate a good leaving grouptrifluoromethanesulfonate group, and then the substitution is conductedby nucleophilic substitution.

(4c)When R⁵ is a hydrogen atom, the oxygen atom can be removed under theconditions of triethylsilane (Et₃SiH) and trifluoroacetic acid.

(5) The protecting group is eliminated to generate the correspondingalcohol:

When the protecting group is a benzyl protecting group, siliconprotecting group, methoxymethyl protecting group (MOM), tetrahydropyranprotecting group (THP), p-methoxyphenyl (PMB) protecting group, etc.,the corresponding method for removing it in the prior art can beselected to remove the protecting group to generate the correspondingalcohol, for example:

(6) The hydroxyl at position R can be subject to many types ofsubstitution to convert to corresponding functional group, such ashalogen, amino, cyano, azide group, trifluoromethanesulfonate group(MsO), p-toluenesulfonate group (TsO), alkenyl, alkynyl, and alkoxy,etc.

(6a) When R is halogen, the following reactions can be conducted, butthey are not limited to these reactions.

(6b) When R is trifluoromethanesulfonate group (MsO) orp-toluenesulfonate group (TsO), an alkaline can react with an alcoholhydroxyl to generate an oxygen anion, which is subsequently subject to anucleophilic substutition by MsCl or TsCl.

(6c) When R is an azide group (N₃), it can be obtained by a nucleophilicsubstitution between sodium azide (NaN₃) and halogen,trifluoromethanesulfonate group (MsO) or p-toluenesulfonate group (TsO):

In the aforementioned equation, X represents a halogen atom,trifluoromethanesulfonate group or p-toluenesulfonate group.

(6d) When R is cyano, it can be obtained by a nucleophilic substitutionbetween a cyanide (such as sodium cyanide, potassium cyanide) andhalogen, trifluoromethanesulfonate group (MsO) or p-toluenesulfonategroup (TsO):

In the aforementioned equation, X represents a halogen atom,trifluoromethanesulfonate group or p-toluenesulfonate group.

(6e) When R is amino group, the azide group or cyano group can bereduced to amino group, or it can be obtained by Gabriel aminesynthesis.

(6f) When R is an alkenyl or alkynyl, it can be obtained by anucleophilic substitution with a nucleophilic agent containing thealkenyl or alkynyl such as RLi, for example:

The branching alkyl chain in the aforementioned compounds as shown inFormula (I) can serve as a solubilizing group for the preparation of theorganic conjugated molecules (especially the organic conjugatedpolymers) and increase the mobility of carriers in the organicconjugated molecule materials. Further, these organic conjugatedmolecules, serving as organic semiconductor materials, can be applied tophotoelectric devices such as organic solar cells, organic lightemitting diodes, and organic field effect transistors, etc.

In the second aspect of the invention, polymers with the aforementionedbranching alkyl chains as shown in the following Formula (II) areprovided:

In Formula (II), Ar¹ and Ar² represent different aromatic compoundfragments; n is an integer which represents the polymerization degree ofthe polymer.

Wherein Ar¹ contains one or more branching alkyl chains in the compoundsas shown in the General Formula (I).

n can, for example, be an integer of 1˜1,000,000, an integer of1˜10,000, or an integer of 1˜1,000.

The polymer is obtained by polymerization of the Ar¹ and Ar² monomers.The polymerization can be conducted by coupling, for example, Suzukicoupling, Stille coupling, Negishi coupling, Sonogashira coupling, Heckcoupling, Kumada coupling, Hiyama coupling, Buchwald-Hartwig couplingand carbon-hydrogen bond activation coupling (Berrouard, P.; Najari, A.;Pron, A.; Gendron, D.; Morin, P.-O.; Pouliot, J.-R.; Veilleux, J.;Leclerc, M. Angew Chem., Int. Ed. 2011, 51, 2068), etc., for example,Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling,Kumada coupling and carbon-hydrogen bond activation coupling.

In an embodiment of the invention, the number of methylenes between thealkyl side chain and the backbone in the polymer, i.e., m>1, forexample, m can be an integer of 2˜18, an integer of 2˜10, an integer of3˜18, an integer of 3˜10, an integer of 3˜5, or an integer of 3˜4. Thiscan effectively reduce the effect of the alkyl chains on the π-πstacking of the polymer backbone, thereby greatly increasing themobility of the polymer.

The polymer as shown in Formula (II) is polymerized from the aromaticcompound monomer having the branching alkyl chains as shown in thefollowing Formula (Ill) and the Ar² aromatic compound monomers. The wavyline in Formula (III) indicates the functional group required by themonomers to polymerize, for example, in order to perform Suzukicoupling, the functional group can be a halogen, boric acid or borate;in order to perform Stille coupling, the functional group can be ahalogen or alkyl tin; in order to perform Sonogashira coupling, thefunctional group can be a halogen or ethynyl; in order to perform Heckcoupling, the functional group can be a halogen or ethenyl; in order toperform Kumada coupling, the functional group is a halogen; in order toperform carbon-hydrogen bond activation coupling, the functional groupcan be a halogen or hydrogen; and in order to perform Hiyama coupling,the functional group can be a halogen or silane.

The aromatic compound as shown in Formula (III) is, for example, thecompounds as shown in the following Formulae III-1 to III-16:

R⁶, R⁷, R⁸, and R⁹ represent substituents on the aromatic ring, forexample, hydrogen atom, halogen atom (such as F, Cl, etc.), nitro,amino, cyano, alkyl, alkenyl, alkynyl, alkoxy, halogen substitutedalkyl, halogen substituted alkoxy, etc.

R¹⁰ and R¹¹ represent one or more substituents on the aromatic ring, forexample, hydrogen atom, halogen atom (such as F, Cl, etc.), nitro,amino, cyano, alkyl, alkenyl, alkynyl, alkoxy, halogen substitutedalkyl, halogen substituted alkoxy, etc.

a and a′ can be independently selected from the following structures:—S—, —O—, —Se—, —NR¹²—, etc.

b, b′, c and c′can be independently selected from the followingstructures: —N═, ═N—, —CR¹²═, ═CR¹²—, etc.

The aforementioned R¹² represents hydrogen atom, alkyl, alkenyl,alkynyl, alkoxy, halogen substituted alkyl, halogen substituted alkoxy,aryl or heteroaryl, etc.;

The aforementioned alkyl can, for example, be C1-C36 linear or branchingalkyl, for example, C1-C18 linear or branching alkyl.

The aforementioned halogen substituted alkyl, can for example, be C1-C36linear or branching halogen substituted alkyl, for example, C1-C18linear or branching halogen substituted alkyl.

The aforementioned alkoxy can, for example, be C1-C36 linear orbranching alkoxy, for example, C1-C18 linear or branching alkoxy.

The aforementioned halogen substituted alkoxy can, for example, beC1-C36 linear or branching halogen substituted alkoxy, for example,C1-C18 linear or branching halogen substituted alkoxy.

The aforementioned alkenyl can, for example, be C2-C18 alkenyl, C2-C10alkenyl, or C2-C6 alkenyl.

The aforementioned alkynyl can, for example, be C2-C18 alkynyl, C2-C10alkynyl, or C2-C6 alkynyl.

The aforementioned aryl can, for example, be phenyl or substitutedphenyl, for example, phenyl.

The aforementioned heteroaryl can, for example, be thienyl, thiazolyl,pyridyl, furyl, for example, thienyl or thiazolyl.

The Ar² aromatic compound monomer can be selected from the followstructures:

wherein the wavy line indicates the functional group required for thepolymerization with the Ar¹ monomers;

a and a′ can be independently selected from the following structures:—S—, —Se—, —O— and —NR¹²—;

b and b′ can be independently selected from the following structures:—N═, ═N—, —SiR¹²═, ═SiR¹²—, —SiR¹²R¹²—, —CR¹²R¹²—CR¹²R¹²— and—CR¹²═CR¹²—;

c can be selected from the following structures: —S—, —S(O)—, —S(O)₂—,—O—, —N═, ═N—, —SiR¹²═, ═SiR¹²—, —SiR¹²R¹²—, —CR¹²R¹²—CR¹²R¹²—,—CR¹²═CR¹²—;

d can be selected from the following structures: —S—, —S(O)—, —S(O)₂—,—O—, —N═, —N—, —SiR¹²═, ═SiR¹²—, —CR¹²R¹²—CR¹²R¹²—, —CR¹²═CR¹²—, —C(O)—and —C(C(CN)₂)—;

g, h, g′ and h′ can be independently selected from the followingstructures: —CR¹²═, ═CR¹²—, —C—, —C(O)— and —C(C(CN)₂)—, —N═ and ═N—;

The aforementioned R¹² can be hydrogen atom, alkyl, alkenyl, alkynyl,alkoxy, halogen substituted alkyl, halogen substituted alkoxy, aryl orheteroaryl etc.;

u is 1, 2, 3 or 4.

The Ar² aromatic compound monomer can, for example, be one of thefollowing structures:

R¹² can be hydrogen atom, alkyl, alkenyl, alkynyl, alkoxy, halogensubstituted alkyl, halogen substituted alkoxy, aryl or heteroaryl, etc.;u is 1, 2, 3 or 4.

The aforementioned Ar² aromatic compound can have one or moresubstituents in its structure.

The synthesis of the Ar¹ aromatic compound having the branching alkylchains can be started from aromatic compounds known in the literature,and obtained by reacting these compounds with the halide and aminocompounds, etc. having the branching alkyl chain structure in thepresent disclosure. Specifically, there are the five following schemes:

(1) When the R in Formula (I) is halogen (X), a nucleophilicsubstitution can occur between X and the following nitrogen-containingaromatic compounds to prepare the aromatic compound in the GeneralFormula (III), for example:

(2) When the R in the General Formula (I) is trifluoromethanesulfonategroup (MsO) or p-toluenesulfonate group (TsO), because these goodleaving groups have similar properties to halogen, they can also be usedin the nucleophilic substitution reaction as shown in (1).

(3) When the R in the General Formula (I) is halogen (X), X is Br or Ifor preparing the corresponding Grignard reagent, thereby directlyobtaining the alkyl substituted aromatic compound via Kumada coupling,for example:

(3) When the R in the General Formula (I) is amino, it can be reactedwith an anhydride to generate a corresponding imide compound, forexample:

The III-6 type compounds can be prepared from III-5 via multi-stepreactions based on the prior art.

(4) When the R in the General Formula (I) is alkenyl, a Heck reactioncan occur between it and an aromatic halide (X=Cl, Br or I) to obtainthe corresponding arylalkenyl derivatives, for example:

(5) When the R in the General Formula (I) is alkynyl, Sonogashirareaction can occur between it and an aromatic halide (X=Cl, Br or I) toobtain the corresponding arylalkynyl derivatives, for example:

In the third aspect of the invention, the aforementioned polymer havingthe branching alkyl chain as shown in Formula (II), serving as anorganic semiconductor material, can be applied to photoelectric devicessuch as organic field effect transistors, organic solar cells, andorganic light emitting diodes, etc., proving that it can greatlyincrease the mobility of carriers in the organic semiconductormaterials.

In the invention, compounds containing a type of novel branching alkylchains have been designed, and effective synthetic schemes of thecompounds containing this type of novel branching alkyl chains have beenraised which enables easy transformation of functional groups. In theinvention, it is further proved that compounds having this type ofbranching alkyl chains can be applied to organic conjugated polymers,and can effectively adjust the π-π stacking between molecules, alsochange the spectral properties and electrochemical properties of thepolymers, and significantly increase the mobility of the organicelectronic materials. Therefore, these results can be widely used in theField of organic electronics, including the field of organicphotovoltaic cells (OPV), organic light emitting diodes (OLED), andorganic field effect transistors, etc.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the effect of the position of the solubilizing group (suchas the alkyl chain) on the π-π stacking of the organic conjugatedpolymers.

FIG. 2 shows the structural diagram of the organic conjugated polymerhaving the branching alkyl chains according to an embodiment of theinvention.

DETAILED DESCRIPTION

The invention is further described in details by way of examples inrelation to figures. However, they are by no means limiting the scope ofthe invention.

Example 1 to Example 3 are Method for Synthesizing Alcohols Protected byBenzyloxy

EXAMPLE 1

Scheme for synthesizing Compound 1: 1,3-propanediol (60 g, 0.79 mol) wasadded into a 500 ml round bottom flask, then solid KOH (17.7 g, 0.32mol) was added to remove the trace moisture in the 1,3-propanediol.Under agitation at 90° C., benzyl chloride (39.8 g, 0.32 mol) was addedinto the 1,3-propanediol using a dropping funnel. Then temperature wasincreased to 130° C. for a 2 h reaction. The reaction was stopped andcooled to the room temperature. After extraction of the organic phaseusing water/diethyl ether separation, the solvent was removed by reducedpressure rotatory evaporation, followed by reduced pressuredistillation. 39.8 g colorless oily product Compound 1 was obtained witha yield of 77%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 7.36-7.28 (m, 5H), 4.51(s, 2H), 3.79-3.75 (m, 2H), 3.66-3.64 (t, J=5.5 Hz, 2H), 2.44 (br, s,1H), 1.88-1.83 (m, 2H).

EXAMPLE 2

Scheme for synthesizing Compound 2: At 0° C., 1,4-butanediol (40 g, 0.44mol) was added into 200 ml dry THF. Sodium hydride (5.3 g, 0.22 mol) wasadded in batches within 30 min. The temperature returned to the roomtemperature for a 2 h reaction. Benzyl bromide (38 g, 0.22 mol) wasdissolved in 20 ml THF, which was dropped into the aforementioned systemat 0° C. followed by reflux for 4 h. After the complete of the reaction,the reaction was quenched with cold water. The organic phase wasextracted with diethyl ether. After drying the organic phase withanhydrous sodium sulfate, it was filtered, then subject to reducedpressure rotatory evaporation to remove the solvent, followed by reducedpressure, distillation to obtain 28.1 g of colorless oily liquid 2 witha yield of 71%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 7.36-7.26 (m, 5H), 4.52(s, 2H), 3.65-3.61 (m, 2H), 3.53-3.50 (t, J=5.3 Hz, 2H), 2.36 (br, s,1H), 1.73-1.65 (m, 4H).

EXAMPLE 3

Scheme for synthesizing Compound 3: At 0° C., 1,5-pentanediol (40 g,0.39 mol) was added into 200 ml dry THF. Sodium hydride (4.6 g, 0.19mol) was added in batches within 30 min. The temperature returned to theroom temperature for a 2 h reaction. Benzyl bromide (33 g, 0.19 mol) wasdissolved in 20 ml THF, which was dropped into the aforementioned systemat 0° C. followed by reflux for 4 h. After the complete of the reaction,the reaction was quenched with cold water. The organic phase wasextracted with diethyl ether. After drying the organic phase withanhydrous sodium sulfate, it was filtered, then subject to rotatoryevaporation to remove the solvent, followed by reduced pressuredistillation to obtain 23.1 g of colorless oily liquid 3 with a yield of62%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 7.36-7.26 (m, 5H), 4.50 (s, 2H),3.64-3.61 (t, J=6.5 Hz, 2H), 3.50-3.64 (t, J=6.5 Hz, 2H), 1.68-1.54 (m,4H), 1.49-1.43 (m, 2H).

Example 4 to Example 6 are the Jones Oxidation and Protection byEsterification of the Alcohols Protected by Benzyloxy

EXAMPLE 4

Scheme for synthesizing Compound 4: Compound 1 (10 g, 60.2 mmol) wasdissolved into 200 ml acetone. At 0° C., Jones reagent (26.72 g chromiumtrioxide : 23 ml concentrated sulfuric acid, diluted with water to 100ml) was added dropwise until the orange red color was sustained withoutturning green. The temperature returned to the room temperature followedby agitation for 2 h. The resultant mixture was vacuum suck filtratedand loaded onto a column which was eluted with acetone. After acetonewas removed by vacuum rotatory evaporation, the organic phases wereextracted with ethyl acetate for three times. The organic phases werecombined and washed once with saturated saline. After dried withanhydrous sodium sulfate and rotatory evaporation, 100 ml ethanol and 2ml concentrated H₂SO₄ were added for 12 h reflux reaction. After mostsolvent was removed by rotatory evaporation, water/ethyl acetate phaseseparation was conducted. The organic phase was washed with sodiumbicarbonate solution, water, and saturated saline respectively, and thendried with anhydrous sodium sulfate. After the solvent was removed byrotatory evaporation, reduced pressure distillation was conducted toobtain 9.7 g colorless oily liquid 4 with a yield of 77%. ¹H NMR (CDCl₃,400 MHz, ppm) δ: 7.36-7.28 (m, 5H), 4.54 (s, 2H), 4.17-4.13 (q, J=7.0Hz, 2H), 3.77-3.74 (t, J=6.2 Hz, 2H), 2.63-2.60 (t, J=6.2 Hz, 2H),1.28-1.24 (t, J=7.1 Hz, 3H).

EXAMPLE 5

Scheme for synthesizing Compound 5: Compound 2 (26.6 g) was dissolvedinto 200 ml acetone. At 0° C., Jones reagent was added dropwise untilthe orange red color was sustained without turning green. Thetemperature returned to the room temperature followed by agitation for 2h. The resultant mixture was vacuum suck filtrated and loaded onto acolumn which was eluted with acetone. After acetone was removed byvacuum rotatory evaporation, the organic phases were extracted withethyl acetate for three times. The organic phases were combined andwashed once with saturated saline. After dried with anhydrous sodiumsulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentratedH₂SO₄ were added for 12 h reflux reaction. After most solvent wasremoved by rotatory evaporation, water/ethyl acetate phase separationwas conducted. The organic phase was washed with sodium bicarbonatesolution, water, and saturated saline respectively, and then dried withanhydrous sodium sulfate. After the solvent was removed by rotatoryevaporation, reduced pressure distillation was conducted to obtain 24.2g colorless oily liquid 5 with a yield of 70%. ¹H NMR (CDCl₃, 400 MHz,ppm) δ: 7.36-7.27 (m, 5H), 4.49 (s, 2H), 4.14-4.08 (q, J=7.1 Hz, 2H),3.52-3.49 (t, J=6.1 Hz, 2H), 2.44-2.40 (t, J=7.3 Hz, 2H), 1.97-1.91 (m,2H), 1.26-1.22 (t, J=7.1 Hz, 3H).

EXAMPLE 6

Scheme for synthesizing Compound 6: Compound 3 (23.1 g) was dissolvedinto 200 ml acetone. At 0° C., Jones reagent was added dropwise untilthe orange red color was sustained without turning green. Thetemperature returned to the room temperature followed by agitation for 2h. The resultant mixture was vacuum suck filtrated and loaded onto acolumn which was eluted with acetone. After acetone was removed byvacuum rotatory evaporation, the organic phases were extracted withethyl acetate for three times. The organic phases were combined andwashed once with saturated saline. After dried with anhydrous sodiumsulfate and rotatory evaporation, 100 ml ethanol and 2 ml concentratedH₂SO₄ were added for 12 h reflux reaction. After most solvent wasremoved by rotatory evaporation, water/ethyl acetate phase separationwas conducted. The organic phase was washed with sodium bicarbonatesolution, water, and saturated saline respectively, and then dried withanhydrous sodium sulfate. After the solvent was removed by rotatoryevaporation, reduced pressure distillation was conducted to obtain acolorless oily liquid 6 with a yield of 62%. ¹H NMR (CDCl₃, 400 MHz,ppm): δ 7.36-7.28 (m, 5H), 4.50 (s, 2H), 4.15-4.09 (q, J=6.8 Hz, 2H),3.50-3.47 (t, J=5.8 Hz, 2H), 2.34-2.30 (t, J=7.0 Hz, 2H), 1.73-1.65 (m,4H), 1.27-1.23 (t, J=6.9 Hz, 3H). ¹³C NMR (CDCl₃, 100 MHz, ppm): δ173.50, 138.48, 128.28, 127.52, 127.44, 72.82, 69.78, 60.14, 34.00,29.11, 21.72, 14.19. ESI-HRMS: Calcd. for [M+H]⁺: 237.14852. Found:237.14859. Calcd. for [M+Na]⁺: 259.13047. Found: 259.13068.

Example 7 to Example 9 are Reactions Between Esters and GrignardReagents:

EXAMPLE 7

Scheme for synthesizing Compound 7: Dry magnesium powders (2.88 g, 120mmol) and an iodine grain were added into a three-necked bottle. Undernitrogen protection, 1-bromodecane (26.5 g, 120 mmol) in diethyl ethersolution was added dropwise under room temperature. After the dropaddition initiated the reaction, a one hour reflux was conducted. Thenunder an ice bath, the diethyl ether solution of Compound 4 was addeddropwise into the system. After 5 h reflux, it was quenched with H₂SO₄(2 M) under ice bath, and then extracted with diethyl ether (3×50 mL).After the organic phases were combined, it was washed with water andsaturated saline. After dried with anhydrous Na₂SO₄ and rotatoryevaporation, it was loaded onto the silica gel column for separation.Compound 7 (12.4 g) was obtained with a yield of 60%. ¹H NMR (CDCl₃, 400MHz, ppm): δ 7.35-7.26 (m, 5H), 4.51 (s, 2H), 3.69-3.66 (t, J=6.0 Hz,2H), 2.98 (s, 1H), 1.79-1.76 (t, J=6.0 Hz, 2H), 1.49-1.37 (m, 4H),1.33-1.15 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H). ¹³C NMR (CDCl₃, 100MHz, ppm) δ: 137.80, 128.36, 127.67, 74.06, 73.34, 67.25, 39.14, 37.73,31.89, 30.27, 29.62, 29.60, 29.32, 23.65, 22.65, 14.07. ESI-HRMS: Calcd.for [M−OH]⁻: 429.40909. Found: 429.40925; Calcd. for [M+Na]⁺: 469.40160.Found: 469.40182. Elemental Anal: Calcd. for C₃₀H₅₄O₂: C, 80.65; H,12.18. Found: C, 80.61; H, 12.16.

EXAMPLE 8

Scheme for synthesizing Compound 8: Dry magnesium powders and an iodinegrain were added into a three-necked bottle. Under nitrogen protection,1-bromodecane in diethyl ether solution was added dropwise under roomtemperature. After the drop addition initiated the reaction, a one hourreflux was conducted. Then under an ice bath, the diethyl ether solutionof Compound 5 was added dropwise into the system. After 5 h reflux, itwas quenched with H₂SO₄ (2 M) under ice bath, and then extracted withdiethyl ether (3×50 mL). After the organic phases were combined, it waswashed with water and saturated saline. After dried with anhydrousNa₂SO₄ and rotatory evaporation, it was loaded onto the silica gelcolumn for separation. Compound 8 was obtained with a yield of 47%. ¹HNMR (CDCl₃, 400 MHz, ppm): δ 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47(t, J=6.3 Hz, 2H), 1.68-1.62 (m, 2H), 1.52-1.48 (m, 2H), 1.43-1.38 (m,4H), 1.32-1.26 (m, 32H), 0.90-0.86 (t, J=6.4 Hz, 6H). ¹³C NMR (CDCl₃,100 MHz, ppm) δ: 138.36, 128.26, 127.51, 127.43, 73.84, 72.83, 70.93,39.20, 36.05, 31.87, 30.25, 29.61, 29.59, 29.30, 23.87, 23.50, 22.63,14.05. ESI-HRMS: Calcd. for [M−OH]⁺: 443.42474. Found: 443.42496; Calcd.for [M+Na]⁺: 483.41725. Found: 483.41761.

EXAMPLE 9

Scheme for synthesizing Compound 9: Dry magnesium powders and an iodinegrain were added into a three-necked bottle. Under nitrogen protection,1-bromodecane in diethyl ether solution was added dropwise under roomtemperature. After the drop addition initiated the reaction, a one hourreflux was conducted. Then under an ice bath, the diethyl ether solutionof Compound 6 was added dropwise into the system. After 5 h reflux, itwas quenched with H₂SO₄ (2 M) under ice bath, and then extracted withdiethyl ether (3×50 mL). After the organic phases were combined, it waswashed with water and saturated saline. After dried with anhydrousNa₂SO₄ and rotatory evaporation, it was loaded onto the silica gelcolumn for separation. Compound 9 was obtained with a yield of 58%. ¹HNMR (CDCl₃, 400 MHz, ppm) δ: 7.35-7.25 (m, 5H), 4.50 (s, 2H), 3.50-3.47(t, J=6.0 Hz, 2H), 1.63-1.57 (m, 2H), 1.40-1.20 (m, 40H), 1.12 (s, 1H),0.90-0.86 (t, J=6.4 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz, ppm) δ: 138.61,128.30, 127.60, 127.45, 74.35, 72.88, 70.27, 39.23, 39.04, 31.90, 30.28,30.26, 29.65, 29.63, 29.61, 29.33, 23.47, 22.67, 20.14, 14.09. ESI-HRMS:Calcd. for [M−OH]⁺: 457.44094. Found: 457.44063; Calcd. for [M+Na]⁺:497.43290. Found: 457.43363.

Example 10 to Example 12 are Deoxygenation and Palladium CarbonCatalyzed Hydrogenation:

EXAMPLE 10

Scheme for synthesizing Compound 10: Compound 7 (12.4 g, 27.8 mmol) wasdissolved into 100 ml dry dichloromethane, to which Et₃SiH (3.54 g, 30.5mmol) and TFA (15.85 g, 139 mmol) were added. After 12 h reaction underthe room temperature, Na₂CO₃ (10 g) was added to quench the reactionuntil no bubble was generated. It was loaded onto a short silica gelcolumn and eluted with dichlorometane, then a rotatory evaporuation wasconducted and followed by it was loaded onto a silica gel column forseparation to obtain a colorless oily liquid. The resultant colorlessoily liquid was dissolved into a mixed solvent of EtOAc/MeOH (100 mL/50mL), to which 5% Pd/C (0.50 g) catalyst was carefully added. Then thereaction was conducted at the room temperature under one atmosphericpressure of hydrogen gas for 24 h. It was loaded onto a flash column andeluted with ethyl acetate, then a rotatory evaporation was conducted andfollowed by it was loaded onto a silica gel column for separation. Acolorless oily liquid 10 was obtained with a yield of 38%. ¹H NMR(CDCl₃, 400 MHz, ppm) δ: 3.68-3.64 (t, J=7.0 Hz, 2H), 1.55-1.50 (q,J=6.8 Hz, 2H), 1.41 (br, s, 1H), 1.32-1.25 (m, 36H), 0.90-0.86 (t, J=6.7Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz, ppm) δ: 61.31, 37.01, 34.27, 33.75,31.92, 30.07, 29.69, 29.65, 29.35, 26.57, 22.69, 14.10. ESI-HRMS: Calcd.for [M+Na]⁺: 363.35974. Found: 363.35895.

EXAMPLE 11

Scheme for synthesizing Compound 11: Compound 8 was dissolved into 100ml dry dichloromethane, to which Et₃SiH and TFA were added. After 12 hreaction under the room temperature, Na₂CO₃ was added to quench thereaction until no bubble was generated. It was loaded onto a shortsilica gel column and eluted with dichlorometane, then a rotatoryevaporuation was conducted and followed by it was loaded onto a silicagel column for separation to obtain a colorless oily liquid. Theresultant colorless oily liquid was dissolved into a mixed solvent ofEtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefullyadded. Then the reaction was conducted at the room temperature under oneatmospheric pressure of hydrogen gas for 24 h. It was loaded onto aflash column and eluted with ethyl acetate, then a rotatory evaporationwas conducted and followed by it was loaded onto a silica gel column forseparation. A colorless oily liquid 11 was obtained with a yield of 67%.¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.64-3.61 (t, J=6.6 Hz, 2H), 1.58-1.50(m, 2H), 1.34-1.24 (m, 39H), 0.90-0.86 (t, J=6.7 Hz, 6H). ¹³C NMR(CDCl₃, 100 MHz, ppm) δ: 63.48, 37.25, 33.61, 31.92, 30.13, 29.97,29.71, 29.66, 29.59, 29.35, 26.67, 22.68, 14.07. ESI-HRMS: Calcd. for[M+Na]⁺: 377.37539. Found: 377.37555.

EXAMPLE 12

Scheme for synthesizing Compound 12: Compound 9 was dissolved into 100ml dry dichloromethane, to which Et₃SiH and TFA were added. After 12 hreaction under the room temperature, Na₂CO₃ was added to quench thereaction until no bubble was generated. It was loaded onto a shortsilica gel column and eluted with dichlorometane, then a rotatoryevaporuation was conducted and followed by it was loaded onto a silicagel column for separation to obtain a colorless oily liquid. Theresultant colorless oily liquid was dissolved into a mixed solvent ofEtOAc/MeOH (100 mL/50 mL), to which 5% Pd/C catalyst was carefullyadded. Then the reaction was conducted at the room temperature under oneatmospheric pressure of hydrogen gas for 24 h. It was loaded onto aflash column and eluted with ethyl acetate, then a rotatory evaporationwas conducted and followed by it was loaded onto a silica gel column forseparation. A colorless oily liquid 12 was obtained with a yield of 60%.¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.66-3.63 (t, J=6.6 Hz, 2H), 1.58-1.51(m, 2H), 1.34-1.23 (m, 41H), 0.90-0.86 (t, J=6.7 Hz, 6H). ¹³C NMR(CDCl₃, 100 MHz, ppm) δ: 63.10, 37.42, 33.63, 33.53, 33.30, 31.93,30.14, 29.72, 29.66, 29.36, 26.71, 22.90, 22.69, 14.10. ESI-HRMS: Calcd.for [M+Na]⁺: 391.39104. Found: 391.39139.

Example 13 to Example 15 are Reactions in Which Hydroxyl is Converted toIodide:

Example 13

Scheme for synthesizing Compound 13: Compound 10 (3.6 g, 10.6 mmol) wasdissolved into dichloromethane, to which imidazole (0.93 g, 13.7 mmol)and triphenylphosphine (3.59 g 13.7 mmol) were added. Under ice bath, 12(3.48 g, 13.7 mmol) was added. After reacting under agitation at theroom temperature for 4 h, Na₂SO₃ (aq.) was added for quenching. Theorganic phase was washed with saturated saline once and dried withanhydrous Na₂SO₄. After rotatory evaporation, it was loaded onto asilica gel column to obtain a colorless oily liquid Compound 13 with ayield of 95%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.21-3.17 (t, J=7.6 Hz,2H), 1.83-1.77 (q, J=7.2 Hz, 2H), 1.40 (s, 1H), 1.33-1.24 (m, 37H),0.90-0.86 (t, J=6.7 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz, ppm): δ 38.64,38.28, 32.88, 31.93, 30.03, 29.69, 29.65, 29.36, 26.41, 22.70, 14.12,5.15. EI-MS: Calcd. for [M−I]⁺: 323. Found: m/z=323. Elemental Anal:Calcd. for C₂₃H₄₇I: C, 61.32; H, 10.62. Found: C, 61.56; H, 10.60.

EXAMPLE 14

Scheme for synthesizing Compound 14: Compound 11 was dissolved intodichloromethane, to which imidazole and triphenylphosphine were added.Under ice bath, 12 was added. After reacting under agitation at the roomtemperature for 4 h, Na₂SO₃ (aq.) was added for quenching. The organicphase was washed with saturated saline once and dried with anhydrousNa₂SO₄. After rotatory evaporation, it was loaded onto a silica gelcolumn to obtain a colorless oily liquid Compound 14 with a yield of75%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.19-3.15 (t, J=7.0 Hz, 2H),1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz,6H). ¹³C NMR (CDCl₃, 100 MHz, ppm) δ: 36.75, 34.60, 33.60, 31.93, 30.97,30.08, 29.70, 29.66, 29.37, 26.66, 22.70, 14.11, 7.62. EI-MS: Calcd. for[M]⁺: 464. Found: m/z=464. Calcd. for [M−I]⁺: 337. Found: m/z=337.Elemental Anal: Calcd. for C₂₄H₄₉I: C, 62.05; H, 10.63. Found: C, 62.35;H, 10.54.

EXAMPLE 15

Scheme for synthesizing Compound 15: Compound 12 was dissolved intodichloromethane, to which imidazole and triphenylphosphine were added.Under ice bath, I₂ was added. After reacting under agitation at the roomtemperature for 4 h, Na₂SO₃ (aq.) was added for quenching. The organicphase was washed with saturated saline once and dried with anhydrousNa₂SO₄. After rotatory evaporation, it was loaded onto a silica gelcolumn to obtain a colorless oily liquid Compound 15 with a yield of94%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.21-3.18 (t, J=7.0 Hz, 2H),1.87-1.77 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 41H), 0.90-0.86 (t, J=6.8 Hz,6H). ¹³C NMR (CDCl₃, 100 MHz, ppm): δ 37.25, 34.01, 33.59, 32.52, 31.94,30.13, 29.71, 29.67, 29.37, 27.65, 26.67, 22.70, 14.12, 7.25. EI-MS:Calcd. for [M−I]⁺: 351. Found: m/z=351. Elemental Anal: Calcd. forC₂₅H₅₁I: C, 62.74; H, 10.74. Found: C. 62.87; H, 10.70.

EXAMPLE 16

Scheme for Synthesizing Compound 16: Dry magnesium powders (3.0 g, 124mmol) and an iodine grain were added into a three-necked bottle. Undernitrogen protection, 1-bromotetradecane (34.3 g, 124 mmol) in diethylether solution was added dropwise under room temperature. After the dropaddition initiated the reaction, a one hour reflux was conducted. Thenunder an ice bath, the ether solution of Compound 5 (11 g, 49.5 mmol)was added dropwise into the system. After 5 h reflux, it was quenchedwith H₂SO₄ (2 M) under ice bath, and then extracted with diethyl ether(3×50 mL). After the organic phases were combined, it was washed withwater and saturated saline. After dried with anhydrous Na₂SO₄ androtatory evaporation, it was loaded onto the silica gel column forseparation. 22.3 g of Compound 16 was obtained with a yield of 79%. ¹HNMR (CDCl₃, 400 MHz, ppm): δ 7.36-7.25 (m, 5H), 4.51 (s, 2H), 3.50-3.47(t, J=6.3 Hz, 2H), 2.98 (s, 1H), 1.69-1.62 (m, 2H), 1.52-1.49 (m, 2H),1.43-1.39 (m, 4H), 1.32-1.26 (m, 48H), 0.90-0.86 (t, J=6.7 Hz, 6H). ¹³CNMR (CDCl₃, 100 MHz, ppm) δ: 138.40, 128.33, 127.58, 127.51, 73.95,72.90, 70.99, 39.24, 36.11, 31.92, 30.29, 29.70, 29.68, 29.65, 29.36,23.92, 23.54, 22.68, 14.11. ESI-HRMS: Calcd. for [M−OH]⁺: 555.54994.Found: 555.55003.

EXAMPLE 17

Scheme for Synthesizing Compound 17: Dry magnesium powders (2.72 g, 113mmol) and an iodine grain were added into a three-necked bottle. Undernitrogen protection, 1-bromooctadecane (37.6 g, 113 mmol) in diethylether solution was added dropwise under room temperature. After the dropaddition initiated the reaction, a one hour reflux was conducted. Thenunder an ice bath, the diethyl ether solution of Compound 5 (10 g, 45mmol) was added dropwise into the system. After 5 h reflux, it wasquenched with H₂SO₄ (2 M) under ice bath, and then extracted withdiethyl ether (3×50 mL). After the organic phases were combined, it waswashed with water and saturated saline. After dried with anhydrousNa₂SO₄ and rotatory evaporation, it was loaded onto the silica gelcolumn for separation. 22.9 g of Compound 17 was obtained with a yieldof 74%. ¹H NMR (CDCl₃, 400 MHz, ppm): δ 7.34-7.26 (m, 5H), 4.51 (s, 2H),3.50-3.47 (t, J=6.3 Hz, 2H), 1.66-1.63 (m, 2H), 1.52-1.48 (m, 2H),1.43-1.39 (m, 4H), 1.32-1.21 (m, 64H), 0.90-0.86 (t, J=6.7 Hz, 6H). ¹³CNMR (CDCl₃, 100 MHz, ppm) δ: 138.39, 128.32, 127.56, 127.49, 73.92,72.89, 70.98, 39.24, 36.11, 31.92, 30.29, 29.70, 29.69, 29.66, 29.36,23.92, 23.54, 22.68, 14.10. ESI-HRMS: Calcd. for [M−OH]⁺: 667.67514.Found: 667.67503.

EXAMPLE 18

Scheme for Synthesizing Compound 18: Compound 16 (22 g, 38.4 mmol) wasdissolved into 250 ml dry dichloromethane, to which Et₃SiH (5.3 g, 46.1mmol) and TFA (21.9 g, 192 mmol) were added. After 12 h reaction underthe room temperature, Na₂CO₃ (10 g) was added to quench the reactionuntil no bubble was generated. It was loaded onto a short silica gelcolumn and eluted with dichlorometane, then a rotatory evaporuation wasconducted and followed by it was loaded onto a silica gel column forseparation to obtain a colorless oily liquid. The resultant colorlessoily liquid was dissolved into a mixed solvent of AcOEt/MeOH (300 mL/200mL), to which 5% Pd/C (1 g) catalyst was carefully added. Then thereaction was conducted at the room temperature under one atmosphericpressure of hydrogen gas for 24 h. It was loaded onto a flash column andeluted with ethyl acetate, then a rotatory evaporation was conducted andfollowed by it was loaded onto a silica gel column for separation. Awhite solid 18 was obtained with a yield of 68%. ¹H NMR (CDCl₃, 400 MHz,ppm) δ: 3.64-3.61 (t, J=6.8 Hz, 2H), 1.58-1.50 (m, 2H), 1.32-1.23 (m,55H), 0.90-0.86 (t, J=6.6 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz, ppm) 63.57,37.24, 33.61, 31.93, 30.13, 29.99, 29.71, 29.67, 29.57, 29.37, 26.67,22.69, 14.10.

EXAMPLE 19

Scheme for Synthesizing Compound 19: Compound 17 (22.9 g, 33.4 mmol) wasdissolved into 250 ml dry dichloromethane, to which Et₃SiH (4.66 g,40.08 mmol) and TFA (19 g, 167 mmol) were added. After 12 h reactionunder the room temperature, Na₂CO₃ (10 g) was added to quench thereaction until no bubble was generated. It was loaded onto a shortsilica gel column and eluted with dichlorometane, then a rotatoryevaporuation was conducted and followed by it was loaded onto a silicagel column for separation to obtain a colorless oily liquid. Theresultant colorless oily liquid was dissolved into a mixed solvent ofAcOEt/MeOH (300 mL/200 mL), to which 5% Pd/C (1 g) catalyst wascarefully added. Then the reaction was conducted at the room temperatureunder one atmospheric pressure of hydrogen gas for 24 h. It was loadedonto a flash column and eluted with ethyl acetate, then a rotatoryevaporation was conducted and followed by it was loaded onto a silicagel column for separation. 12.9 g of white solid 19 was obtained with ayield of 67%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.63-3.60 (t, J=6.6 Hz,2H), 1.57-1.51 (m, 2H), 1.32-1.24 (m, 71H), 0.90-0.86 (t, J=6.8 Hz, 6H).¹³C NMR (CDCl₃, 100 MHz, ppm) δ: 63.52, 37.26, 33.62, 31.95, 30.16,29.99, 29.74, 29.69, 29.59, 29.39, 26.69, 22.70, 14.10.

EXAMPLE 20

Scheme for synthesizing Compound 20: Compound 18 (8.92 g, 19.1 mmol) wasdissolved into dichloromethane, to which imidazole (1.56 g, 22.9 mmol)and triphenylphosphine (6.0 g, 22.9 mmol) were added. Under ice bath, I₂(5.82 g, 22.9 mmol) was added. After reacting under agitation at theroom temperature for 4 h, Na₂SO₃ (aq.) was added for quenching. Theorganic phase was washed with saturated saline once and dried withanhydrous Na₂SO₄. After rotatory evaporation, it was loaded onto asilica gel column to obtain 10.8 g of colorless oily liquid Compound 20with a yield of 98%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.19-3.15 (t, J=7.0Hz, 2H), 1.83-1.76 (m, 2H), 1.32-1.22 (m, 55H), 0.90-0.86 (t, J=6.6 Hz,6H). EI-MS: Calcd. for [M]⁺: 576. Found: m/z=576.

EXAMPLE 21

Scheme for synthesizing Compound 21: Compound 19 (11.27 g, 19.46 mmol)was dissolved into dichloromethane, to which imidazole (1.59 g, 23.4mmol) and triphenylphosphine (6.14 g, 23.4 mmol) were added. Under icebath, 12 (5.93 g, 23.4 mmol) was added. After reacting under agitationat the room temperature for 4 h, Na₂SO₃ (aq.) was added for quenching.The organic phase was washed with saturated saline once and dried withanhydrous Na₂SO₄. After rotatory evaporation, it was loaded onto asilica gel column to obtain 13.17 g of colorless oily liquid Compound 21with a yield of 98%. ¹H NMR (CDCl₃, 400 MHz, ppm) 5: 3.18-3.15 (t, J=7.0Hz, 2H), 1.83-1.76 (p, J=7.1 Hz, 2H), 1.33-1.22 (m, 71H), 0.90-0.86 (t,J=6.6 Hz, 6H). ¹³C NMR (CDCl₃, 100 MHz, ppm) δ: 36.75, 34.60, 33.61,31.96, 30.97, 30.10, 29.74, 29.72, 29.70, 29.40, 26.67, 22.72, 14.13,7.55. EI-MS: Calcd. for [M]⁺: 688. Found: m/z=688.

EXAMPLE 22

Scheme for synthesizing Compound 22: Compound 14 (1.0 g, 2.15 mmol) wasdissolved into 100 ml DMF. At the room temperature, sodium azide (0.7 g,10.5 mmol) was added in batches. After reaction under agitation at 85°C. for 4 h, DMF was removed by vacuum distillation. Extraction wasconducted with petroleum ether. The organic phase was washed withsaturated saline once and dried with anhydrous Na₂SO₄. The solvent wasremoved by vacuum to obtain the product 22 (0.81 g) with a yield of100%. ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 3.26-3.22 (t, J=7.0 Hz, 2H),1.81-1.76 (p, J=7.1 Hz, 2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz,6H). EI-MS: Calcd. for [M]⁺: 379. Found: m/z=379.

EXAMPLE 23

Scheme for synthesizing Compound 23: Compound 22 (0.81 g, 2.15 mmol) wasdissolved in 100 ml petroleum ether. Pd/C (0.1 g) was added. At the roomtemperature, hydrogenation was conducted for 12 h, followed byfiltration with kieselguhr and column separation to obtain 0.6 g ofcolorless oily liquid Compound 23 with a yield of 80%. ¹H NMR (CDCl₃,400 MHz, ppm) δ: 3.26-3.22 (t, J=7.0 Hz, 2H), 1.81-1.76 (p, J=7.1 Hz,2H), 1.40-1.22 (m, 39H), 0.90-0.86 (t, J=6.8 Hz, 6H). EI-MS: Calcd. for[M]⁺: 354. Found: m/z=354.

Example 24 to Example 28 are Reactions for Preparing the Monomers forPolymerization:

EXAMPLE 24

Synthesis of Monomer M2: 6,6′-dibromoisoindigo (1.70 g, 4.04 mmol) andpotassium carbonate (1.68 g, 12.1 mmol) were dissolved in DMF (100 mL).Compound 13 (4.19 g, 9.31 mmol) was added under nitrogen protection.Reaction was conducted under agitation at temperature of 100° C. for 15h. After the complete of the reaction, the solvent was removed byrotatory evaporation. After solvation into CHCl₃ (100 mL) and washedwith water for three times, the organic phases were combined and washedwith saturated saline once, and then dried with anhydrous Na₂SO₄. Afterrotatory evaporation, it was loaded onto a silica gel column forseparation to obtain 3.79 g of dark red solid M2 with a yield of 88%. ¹HNMR (CDCl₃, 400 MHz, ppm) δ: 9.09-9.07 (d, J=8.6 Hz, 2H), 7.17-7.15 (dd,J₁=8.6 Hz, J₂=1.6 Hz, 2H), 6.89-6.88 (d, J=1.6 Hz, 2H), 3.74-3.70 (t,J=7.4 Hz 4H), 1.71-1.56 (q, J=6.3 Hz, 4H), 1.42-1.26 (m, 74H), 0.90-0.86(t, J=6.8 Hz, 4H).¹³C NMR (CDCl₃, 100 MHz, ppm): δ 167.49, 145.68,132.55, 131.22, 126.66, 125.05, 120.44, 111.18, 55 38.39, 35.61, 33.44,31.93, 30.96, 30.04, 29.70, 29.69, 29.66, 29.36, 26.62, 22.70, 14.12.Elemental Anal: Calcd. for C₆₂H₁₀₀Br₂N₂O₂: C, 69.90; H, 9.46; N, 2.63.Found: C, 69.78; H, 9.46; N, 2.62. ESI-HRMS: Calcd. for [M+H]⁺:1063.62243. Found: 1063.62480.

EXAMPLE 25

Synthesis of Monomer M3: 6,6′-dibromoisoindigo and potassium carbonatewere dissolved in DMF (100 mL). Compound 14 was added under nitrogenprotection. Reaction was conducted under agitation at temperature of100° C. for 15 h. After the complete of the reaction, the solvent wasremoved by rotatory evaporation. After dissolved into CHCl₃ (100 mL) andwashed with water for three times, the organic phases were combined andwashed with saturated saline once, and then dried with anhydrous Na₂SO₄.After rotatory evaporation, it was loaded onto a silica gel column forseparation to obtain a dark red solid M3 with a yield of 71%. ¹H NMR(CDCl₃, 400 MHz, ppm) δ: 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.16 (dd,J₁=8.6 Hz, J₂=1.6 Hz, 2H), 6.93-6.92 (d, J=1.6 Hz, 2H), 3.73-3.69 (t,J=7.4 Hz, 4H), 1.68-1.64 (m, 4H), 1.34-1.22 (m, 78H), 0.89-0.86 (t,J=6.6 Hz, 12H). ¹³C NMR (CDCl₃, 100 MHz, ppm): δ 167.68, 145.76, 132.60,131.21, 126.72, 125.10, 120.41, 111.28, 40.61, 37.10, 33.52, 31.93,30.81, 30.09, 29.69, 29.65, 29.36, 26.67, 24.47, 22.69, 14.12. ElementalAnal: Calcd. for C₆₄H₁₀₄Br₂N₂O₂: C, 70.31; H, 9.59; N, 2.56. Found: C,70.50; H, 9.62; N, 2.53. ESI-HRMS: Calcd. for [M+H]⁺: 1091.65373. Found:1093.65487.

EXAMPLE 26

Synthesis of Monomer M4: 6,6′-dibromoisoindigo and potassium carbonatewere dissolved in DMF (100 mL). Compound 15 was added under nitrogenprotection. Reaction was conducted under agitation at temperature of100° C. for 15 h. After the complete of the reaction, the solvent wasremoved by rotatory evaporation. After dissolved into CHCl₃ (100 mL) andwashed with water for three times, the organic phases were combined andwashed with saturated saline once, and then dried with anhydrous Na₂SO₄.After rotatory evaporation, it was loaded onto a silica gel column forseparation to obtain a dark red solid M4 with a yield of 83%. ¹H NMR(CDCl₃, 400 MHz, ppm) δ: 9.10-9.07 (d, J=8.6 Hz, 2H), 7.17-7.14 (dd,J₁=8.6 Hz, J₂=1.6 Hz, 2H), 6.92-6.91 (d, J=1.6 Hz, 2H), 3.74-3.70 (t,J=7.4 Hz, 4H), 1.67-1.62 (m, 4H), 1.36-1.22 (m, 82H), 0.89-0.86 (t,J=6.8 Hz, 12H). ¹³C NMR (CDCl₃, 100 MHz, ppm): δ 167.67, 145.76, 132.59,131.23, 126.71, 125.10, 120.41, 111.26, 40.27, 37.39, 33.61, 33.36,31.93, 30.13, 29.72, 29.66, 29.37, 27.78, 26.71, 24.22, 22.70, 14.12.Elemental Anal: Calcd. for C₆₆H₁₀₈Br₂N₂O₂: C, 70.69; H, 9.71; N, 2.50.Found: C, 70.79; 11, 9.55; N, 2.49. ESI-HRMS: Calcd. for [M+Na]⁺:1141.66698. Found: 1141.66836.

EXAMPLE 27

Synthesis of Monomer M5: 6,6′-dibromoisoindigo (2 g, 4.76 mmol) andpotassium carbonate (1.97 g, 14.28 mmol) were dissolved in DMF (100 mL).Compound 20 (6.0 g, 10.4 mmol) was added under nitrogen protection.Reaction was conducted under agitation at temperature of 100° C. for 15h. After the complete of the reaction, the solvent was removed byrotatory evaporation. After dissolved into CHCl₃ (100 mL) and washedwith water for three times, the organic phases were combined and washedwith saturated saline once, and then dried with anhydrous Na₂SO₄. Afterrotatory evaporation, it was loaded onto a silica gel column forseparation to obtain 6.0 g of dark red solid M5 with a yield of 95%. ¹HNMR (CDCl₃, 400 MHz, ppm) δ: 9.10-9.08 (d, J=8.6 Hz, 2H), 7.18-7.15 (dd,J₁=8.6 Hz, J₂=1.81 Hz, 2H), 6.93-6.92 (d, J=1.8 Hz, 2H), 3.73-3.69 (t,J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22 (m, 114H), 0.89-0.86 (t,J=6.6 Hz, 12H).

EXAMPLE 28

Synthesis of Monomer M6: 6,6′-dibromoisoindigo (1.5 g, 3.57 mmol) andpotassium carbonate (1.48 g, 10.71 mmol) were dissolved in DMF (100 mL).Compound 21 (5.41 g, 7.86 mmol) was added under nitrogen protection.Reaction was conducted under agitation at temperature of 100° C. for 15h. After the complete of the reaction, the solvent was removed byrotatory evaporation. After dissolved into CHCl₃ (100 mL) and washedwith water for three times, the organic phases were combined and washedwith saturated saline once, and then dried with anhydrous Na₂SO₄. Afterrotatory evaporation, it was loaded onto a silica gel column forseparation to obtain 4.95 g of dark red solid M6 with a yield of 90%. ¹HNMR (CDCl₃, 400 MHz, ppm) ¹H NMR (CDCl₃, 400 MHz, ppm) δ: 9.10-9.08 (d,J=8.6 Hz, 2H), 7.18-7.15 (dd, J₁=8.6 Hz, J₂=1.8 Hz, 2H), 6.93-6.92 (d,J=1.8 Hz, 2H), 3.73-3.69 (t, J=7.5 Hz, 4H), 1.67-1.64 (m, 4H), 1.34-1.22(m, 142H), 0.89-0.86 (t, J=6.6 Hz, 12H).

Example 29 to Example 31 are Polymerization for the Polymers:

EXAMPLE 29

Synthesis of Polymer P2: Under nitrogen protection, M2 (0.235 mmol),5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.235 mmol), Pd₂(dba)₃ (4.3mg, 2 mol %), P(o-tol)₃ (5.7 mg, 8 mol %), and 10 ml dry toluene solventwere added into a reaction flask. After reaction with agitation attemperature of 110° C. for 24 h, Soxhlet extraction was conducted withchloroform to obtain the product (236 mg, with a yield of 95%).Elemental Anal. Calcd: for (C₇₀H₁₀₄N₂O₂S₂)_(n): C, 78.52; H, 9.88; N,2.62. Found: C, 77.78; H, 9.47; N, 2.55.

EXAMPLE 30

Synthesis of Polymer P3: Under nitrogen protection, M3 (0.229 mmol),5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.229 mmol), Pd₂(dba)₃ (4.3mg, 2 mol %), P(o-tol)₃ (5.6 mg, 8 mol %), and 10 ml dry toluene solventwere added into a reaction flask. After reaction with agitation attemperature of 110° C. for 24 h, Soxhlet extraction was conducted withchloroform to obtain the product (238 mg, with a yield of 94%).Elemental Anal. Calcd: for (C₇₂H₁₀₈N₂O₂S₂)_(n): C, 77.78; H, 9.92; N,2.55. Found: C, 77.85; H, 9.75; N, 2.48.

EXAMPLE 31

Synthesis of Polymer P4: Under nitrogen protection, M4 (0.229 mmol),5,5′-bis(trimethylstannyl)-2,2′-bithiophene (0.229 mmol), Pd₂(dba)₃ (4.2mg, 2 mol %), P(o-tol)₃ (5.6 mg, 8 mol %), and 10 ml dry toluene solventwere added into a reaction flask. After reaction with agitation attemperature of 110° C. for 24 h, Soxhlet extraction was conducted withchloroform to obtain the product (220 mg, with a yield of 87%).Elemental Anal. Calcd. for (C₇₄H₁₁₂N₂O₂S₂)_(n): C, 78.95; H, 10.03; N,2.49. Found: C, 78.25; H, 9.91; N, 2.46.

EXAMPLE 32

The optical physical properties and electrochemical properties ofPolymers P2, P3, and P4 were characterized and the data are shown in thefollowing table:

TABLE 1 The optical physical and electrochemical properties of PolymersP1-P4 Molecular Weight Decomposition M_(n) Temperature λ_(max) sol.λ_(max) film E_(g) ^(opt) E_(HOMO) E_(LUMO) E_(g) ^(cv) E_(HOMO PES)Polymer (kDa)/PDI (° C.) (nm)^(a) (nm)^(b) (eV)^(c) (eV)^(d) (eV)^(d)(eV)^(e) (eV)^(f) P1 20.4/2.0 390 706, 647 701, 637 1.60 −5.70 −3.702.00 −5.54 P2 18.4/2.0 384 711, 647 707, 641 1.60 −5.60 −3.70 1.90 −5.57P3 39.2/3.2 392 718, 673 719, 653 1.58 −5.52 −3.74 1.78 −5.33 P437.3/2.3 374 719, 675 716, 647 1.58 −5.50 −3.74 1.76 −5.26 ^(a)Longestabsorption wavelength of the solution (corresponding to 0-0 vibrationabsorption and 0-1 vibration absorption, respectively), ^(b) longestabsorption wavelength of the film (corresponding to 0-0 vibrationabsorption and 0-1 vibration absorption, respectively); ^(c) band gap inthe absorption spectrum; ^(d) electrochemical measurement value; ^(e)electrochemical band gap; ^(f) photoelectron spectrum (PES) measurementvalue.

Among them, P1 is a 2-branching polymer (Lei, T.; Cao, Y.; Fan, Y.; Liu,C. J.; Yuan, S. C.; Pei, J. J. Am. Chem. Soc. 2011, 133, 6099), whosestructure is as follows:

P2˜P4 are polymers synthesized in the invention. After the introductionof different branching alkyl chains, significant change occurred to thespectra and electrochemistry of P2˜P4. The absorption spectra apparentlyshifted to red, the HOMO energy levels apparently increased, and theband gaps apparently reduced. These changes were due to the changes ofthe mode of stacking between polymers.

EXAMPLE 33

Device processing and X-ray diffraction characterization of the organicfield effect transistor comprising polymers P1-P4:

Processing of the organic field effect transistor (OTFT) was conductedwith the device structure of bottom-gate/top-contact (BG/TC). For thesubstrate, doped silicon (n⁺⁺-Si) was used as a gate electrode, and 300nm silicon dioxide was used as an insulation layer. The substrate waswashed with acetone, a detergent, water and isopropanol successivelybefore dried with nitrogen blow. Then the substrate was cleaned withplasma beam for 15 minutes, and modified with octadecylsilane. Then thedichlorobenzene solution of the polymer was spin coated onto thesubstrate and annealed at different temperatures. Then at high vacuum, alayer of 30 mm gold electrode was coated by hot vapor deposition with aphysical mask as the source electrode and the drain electrode. Themeasurement of the mobility of the polymer was conducted on a Keithley4200 semiconductor characterization system.

The experiments proved that compared to P1, the mobility of P3 had greatincrease from the initial 0.79 cm²V⁻¹s⁻¹ (P1) to 3.62 cm²V⁻¹s⁻¹. Thethreshold voltage also significantly decreased.

The X ray diffraction experiment was conducted on Beamline BLI4B1 atShanghai Synchrotron Radiation Facility with a wavelength of 1.2398 Å,and the measurement was conducted with an NaI counter. The experimentsproved that the type of branching alkyl chains contained in the polymerseffectively reduced the π-π stacking distance between polymers. Thisresult also proved the huge effect of the novel alkyl chain of thedisclosure in organic semiconductor devices.

TABLE 2 Performance of the organic field effect transistors and resultsof the film glancing X-ray study Annealing Threshold on/off TemperatureMobility Voltage ratio d(Å)^(b) Polymer (° C.) (cm²V⁻¹s⁻¹)^(a) (V)I_(on)/I_(off) L π P1 150 0.79 (0.45) −18 >10⁶ 20.3 3.75 P2 200 0.40(0.28) −10 >10⁵ 23.7 3.61 P3 175 3.62 (2.98) −2 >10⁶ 24.7 3.57 P4 1751.76 (1.44) −5 >10⁶ 26.1 3.57 ^(a)The measurement was conducted in air(RH = 50~60%). Maximal mobility values were shown outside theparentheses, while average values were shown in the parentheses. ^(b)Thelayer phase distance (L) and π-π stacking distance (π) obtained in theX-ray study.

1. A Formula (I) compound:

in the structure of Formula (I), m is an integer from 3 to 18; R is ahalogen atom, hydroxyl, amino, trifluoromethanesulfonate group,p-toluenesulfonate group, azide group, cyano, alkenyl, alkynyl oralkoxy; R³ and R⁴ are the same or different, independently selected fromalkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy,alkenyl and alkynyl; R⁵ is hydrogen, hydroxyl, alkyl, halogensubstituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl oralkynyl.
 2. The Formula (I) compound according to claim 1, wherein m isan integer from 3 to
 4. 3. The Formula (I) compound according to claim1, wherein the compound is selected from one of the following compounds:


4. The method for preparation the Formula (I) compound according toclaim 1 comprising the following steps: 1) Starting from the diol asshown in Formula (a), protection by a protecting group is conducted toobtain the diol with one terminus protected as shown in Formula (b);

2) The diol with one terminus protected is oxidized to obtain thecarboxylic acid as shown in Formula (c);

3) The carboxylic acid as shown in Formula (c) is subject to functionalgroup transformation and nucleophilic substitution to introduce the R³and R⁴ groups;

4) R⁵ is introduced;

5) The protecting group is eliminated to generate the correspondingalcohol;

6) When the R in Formula (I) is not hydroxyl, a substitution isconducted on the hydroxyl in the Formula (k) compound to convert it toother functional group, obtaining the Formula (1) compound with R beingthe corresponding functional group, wherein m−1 is an integer of from 3to 18 or from 3 to 4; R³ and R⁴ are the same or different, independentlyselected from alkyl, halogen substituted alkyl, alkoxy, halogensubstituted alkoxy, alkenyl and alkynyl; R⁵ is hydrogen, hydroxyl,alkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy,alkenyl or alkynyl.
 5. The method of preparation according to claim 4,wherein the step 3) is conducted with the following method 3a) or 3b):3a) The carboxylic acid is reacted with an alcohol and converted into anester, followed by a nucleophilic substitution to introduce the R³ andR⁴ groups:

wherein R¹ is alkyl; 3b) The carboxylic acid is converted to an acylhalide, then the nucleophilic substitution is conducted to introduce theR³ and R⁴ groups:

wherein X is halogen, wherein m−1 is an integer of from 3 to 18 or from3 to 4; R³ and R⁴ are the same or different, independently selected fromalkyl, halogen substituted alkyl, alkoxy, halogen substituted alkoxy,alkenyl and alkynyl.
 6. The method of preparation according to claim 4,wherein the step 4) is conducted with the following method 4a), 4b) or4c): 4a) When R⁵ is alkoxy, a strong alkaline is reacted with thealcohol hydroxyl of the Formula (e) compound to generate an oxygenanion, which is subsequently subject to a nucleophilic substutition byR⁵′X to obtain the compound of Formula (g):

wherein OR⁵′ is R⁵; X is a halogen atom, trifluoromethanesulfonate groupor p-toluenesulfonate group; and R⁵′ is alkyl; 4b) When R⁵ is alkyl,halogen substituted alkoxy, alkenyl or alkynyl, the Formula (e) compoundis reacted with trifluoromethanesulfonyl chloride to generatetrifluoromethanesulfonate group, and then a nucleophilic substitution isconducted to obtain the Formula (i) compound:

4c) When R⁵ is hydrogen atom, the oxygen atom is removed under theconditions of triethylsilane and trifluoroacetic acid to form theFormula (j) compound,

wherein m−1 is an integer of from 3 to 18 or from 3 to 4; R³ and R⁴ arethe same or different, independently selected from alkyl, halogensubstituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl andalkynyl.
 7. The method of preparation according to claim 4, wherein thestep 6) is conducted using one of the following method 6a)˜6f) dependingon different substituents of R: 6a) When R is halogen, one of thefollowing reactions is conducted to obtain the corresponding Formula (I)compound:

6b) When R is trifluoromethanesulfonate group or p-toluenesulfonategroup, an alkaline is reacted with the alcohol hydroxyl to generate anoxygen anion, which is subsequently subject to a nucleophilicsubstutition by MsCl or TsCl to obtain the corresponding Formula (1)compound;

6c) When R is an azide group, the Formula (I) compound with R being anazide group is obtained by a nucleophilic substitution between sodiumazide and halogen, trifluoromethanesulfonate group or p-toluenesulfonategroup:

In the aforementioned reaction, X represents a halogen atom,trifluoromethanesulfonate group or p-toluenesulfonate group; 6d) When Ris cyano, the Formula (I) compound with R being a cyano is obtained by anucleophilic substitution between a cyanide and halogen,trifluoromethanesulfonate group or p-toluenesulfonate group:

In the aforementioned reaction, X represents a halogen atom,trifluoromethanesulfonate group or p-toluenesulfonate group; 6e) When Ris amino, the Formula (I) compound with R being an amino is obtained bythat the azide group or cyano is reduced to amino, or a Gabriel aminesynthesis:

In the aforementioned reaction, X represents a halogen atom,trifluoromethanesulfonate group or p-toluenesulfonate group; 6f) When Ris an alkenyl or alkynyl, the Formula (1) compound with R being alkenylor alkynyl is obtained by a nucleophilic substitution of the Formula (I)compound with R being a halogen atom by a nucleophilic agent containingthe alkenyl or alkynyl, wherein m−1 is an integer of from 3 to 18 orfrom 3 to 4; R³ and R⁴ are the same or different, independently selectedfrom alkyl, halogen substituted alkyl, alkoxy, halogen substitutedalkoxy, alkenyl and alkynyl; R⁵ is hydrogen, hydroxyl, alkyl, halogensubstituted alkyl, alkoxy, halogen substituted alkoxy, alkenyl oralkynyl.